Method of content protection with durable UV absorbers

ABSTRACT

The contents of clear or lightly colored plastic containers or films are protected from ultraviolet radiation by the incorporation of certain UV absorbers of the class of durable benzotriazoles and tris-aryl-s-triazines in the container or film. Contents to be protected include foodstuffs, beverages, pharmaceuticals, cosmetics, personal care products, shampoos and the like.

[0001] This application claims the benefit under 35 USC 119(e) of U.S.Provisional Application Serial No. 60/179,567 filed on Feb. 1, 2000.

[0002] The present invention relates to the protection of foodstuffs,beverages, pharmaceuticals, cosmetics, personal care products, shampoosand the like from the deleterious effects of ultraviolet radiation. Ithas been found that certain highly durable benzotriazoles andtris-aryl-s-triazines are especially effective towards this end whenincorporated in the containers or films in which such materials arestored.

[0003] Many products such as certain fruit juices, soft drinks, beer,wines, food products, dairy products, cosmetics, shampoos, vitamins andpharmaceuticals are deleteriously affected, i.e. degraded, by theeffects of ultraviolet (UV). light when packaged in plastic containerswhich allow the transmission of such light.

[0004] The use of UV absorbers towards protecting bottle and filmcontents is well known However there is a trend towards the use of clearor lightly colored containers. More aesthetically pleasing containersmay be formed from clear plastics which also allow one to view thecontents. Unfortunately, clear and lightly colored containers and filmsallow the transmission of significant portions of ultraviolet light,i.e. light in the range of about 280 to about 400 nm. Further, there isa trend towards more light-weight and hence thinner walled containers.Thin-walled containers, by virtue of a shorter path length, will allowmore UV light to pass. Due to these trends in packaging there is a needfor more efficient UV absorbers for use in this area UV absorberefficiency is a function of how strongly the molecule absorbs lightacross the entire UV region as well as its thermal and photostability,i.e. durability.

[0005] Many cooking oils and salad oils are now offered in clear PET[poly(ethylene terephthalate)] packaging. Practically all vegetable orseed-based oils such as soybean, olive, safflower, cottonseed and cornoils contain varying levels of unsaturated olefinic acids or esters(e.g. linoleates) which are susceptible to light-induced degradation.Most plant based oils also contain natural chlorophyll or other pigmentphotosensitizers. Pascall, et al., J Food Sci., 60 (5), 1116 (1995),discuss the UV protection of soybean oil with the use of Tinuvine® 326incorporated into coextruded, multi-layered, polypropylene-basedcontainers. Tinuvin® 326 is a benzotriazole UV absorber,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole,available from Ciba Specialty Chemicals Corp.

[0006] Milk is packaged in translucent or white pigmented HDPE bottlesto reduce the amount of light transmission through the plastic. Fanelli,et al., J. Food Protection, 48(2), 112-117 (1985) disclose that Tinuvine326 in HDPE packaging is effective at reducing the loss rate of VitaminA in milk exposed to cool white fluorescent light. Protection ofvitamins is also of importance in fruit juices. In “Tropicana TwistsAgain,” Packaging World, Jan. 1999, p.2, it is disclosed that PETbottles containing a “UV inhibitor” are used to protect the shelf lifeof Vitamin C in fruit drinks.

[0007] The use of Tinuvin® 234,2-(2-hydroxy-3,5-di-α-cumyl)-2H-benzotriazole, Tinuvin® 326,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole,Tinuvin® 327,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, andTinuvin® 1577, 4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine,in packaging for content protection is known. In particular, thecombinations of Tinuvin® 234 with either Tinuvin® 327 or Tinuvin® 326are known.

[0008] It is well known that beer is normally bottled in amber orgreen-tinted glass to protect it from light. A highly efficient UVabsorber would allow beer to be packaged in, for example, clear PETbottles.

[0009] U.S. Pat. Nos. 4,882,412, 4,892,923 and 4,950,732 disclose theuse of 7-oxy-2H-1-benzopypran-2-one, 7-oxy-2H-1-benzopyran-2-imine,3H-naphtho[2,1-b]pyran-3-one, 3H-naphtho[2,1-b]pyran-3-imine andbis-methine moieties as UV absorbing groups to protect the contents ofpolyester and polycarbonate containers.

[0010] U.S. Pat. No. 5,948,458 teaches the protection of foodscontaining unsaturated lipids and fats from spoilage due to exposure toUV radiation by incorporation of calcium phosphate compounds eitherdirectly into the food product itself or in the food coatings andpackage wrap.

[0011] It has been found that certain UV absorbers of the class ofdurable benzotriazoles and tris-aryl-s-triazines are especiallyeffective towards protecting the contents of clear, lightly colored andthin-walled containers and films.

[0012] The description, preparation and uses of the 2H-benzotriazole UVabsorbers are described in U.S. Pat. Nos. 3,004,896; 3,055,896;3,072,585; 3,074,910; 3,189,615; 3,230,194; 4,127,586; 4,226,763;4,278,589; 4,315,848; 4,383,863; 4,675,352; 4,681,905 and 4,853,471.

[0013] U.S. Pat. Nos. 5,319,091 and 5,410,071 described the preparationof benzotriazoles substituted at the 5-position of the benzo ring withalkyl- or aryl-sulfonyl moieties. It is taught in U.S. Pat. No.5,280,124 that by introducing a higher alkyl or aryl sulfoxide orsulfone at the 5-position of the benzo ring of the benzotriazole, theresulting benzotriazole exhibits enhanced absorption in the near visiblerange (over 350 nm). Such sulfone substituted products were shown to beuseful in automotive coatings applications. U.S. Pat. Nos. 5,977,219 and6,166,218 teach that an electron withdrawing moiety at the 5-position ofthe benzo ring of the benzotriazole is advantageous for similar reasons.Additionally, this patent and copending application teach that such anelectron withdrawing group dramatically increases the photostability ofthese benzotriazole UV absorbers in automotive coatings. U.S. Pat. No.5,574,166 teaches that benzotriazoles with a cumyl group ortho to thephenol are especially thermally stable. Surprisingly, these highlydurable benzotriazoles are especially well-suited for the instantapplications.

[0014] U.S. Pat. No. 3,218,332 discloses benzotriazoles substituted atthe 5-position of the benzo ring by a lower alkyl sulfonyl moiety. U.S.Pat. Nos. 5,268,450 and 5,319,091 disclose polymer compositions and aprocess for the production of substituted aryl thio and aryl sulfonylbenzotriazoles which are covalently bound to polymers, such aspoly(phenylene sulfide), RYTON®, Phillips Petroleum. U.S. Pat. No.5,280,124 discloses benzotriazoles with only higher alkyl or arylsulfinyl or sulfonyl moieties at the 5-position of the benzo ring whichare useful for protecting thermoset automotive coatings. U.S. Pat. No.5,977,219 and the copending patent application mentioned above teach theuse of certain electron withdrawing groups including some sulfonylgroups at the 5-position of the benzo ring for the stabilization ofautomotive coatings.

[0015] Japanese Patent No. 92-352228 discloses the use of5-ethylsulfonyl benzotriazoles with the 3-position of the phenyl ringbeing unsubstituted or substituted by methyl for the UV protection ofdust proof poly(vinyl chloride) resin films.

[0016] Copending application Ser. No. 09/303,583 teaches the use of thisclass of UV absorbers in adhesive compositions suitable for use as anadhesive layer in a laminated article or multi-layer construction. Thelaminated articles include solar control films, films and glazings, UVabsorbing glasses and glass coatings, optical films and the like. Theprotection of interior structures, textiles and fabrics from UV inducedphotodegradation such as in automotive applications is discussed.

[0017] The description, preparation and uses of the s-triazine UVabsorbers are described for automotive coatings, photographicapplication, polymeric film coatings and ink jet printing. Automotivecoatings are described in British 2,317,174A and 2,317,893A and in U.S.Pat. Nos. 5,354,794; 5,556,973; 5,681,955; 5,726,309 and 5,106,891.Photographic applications are disclosed in U.S. Pat. No. 3,843,371 andcopending application Ser. No. 08/974,263. Polymeric film coatings aredescribed in U.S. Pat. Nos. 4,619,956 and 4,740,542. Ink jet printing isdisclosed in U.S. Pat. No. 5,096,489. Tris-aryl-s-triazines with highmolar absorption are described in copending application Ser. No.09/383,163. From each of these patents, the s-triazine UV absorbers arerevealed as very photostable.

[0018] The s-triazine UV absorbers can be prepared by the generalsynthetic procedures outlined in U.S. Pat. Nos. 5,726,309; 5,681,955 and5,556,973; British 2,317,714A, WO 96/28431 and EP 941989A2.

[0019] It is known in the art that the concomitant use of a hinderedamine light stabilizer with a UV absorbers such as benzotriazoles ands-triazines provide excellent stabilization in many polymer compositionsas summarized by G. Bemer and M. Rembold, “New Light Stabilizers forHigh Solids Coatings”, Organic Coatings and Science and Technology, Vol.6, Dekkar, N.Y., pp 55-85.

DETAILED DISCLOSURE

[0020] The instant invention pertains to plastic containers or films forcontent storage which protect the contents therein against thedeleterious effects of ultraviolet radiation which comprise

[0021] (a) a clear or lightly colored plastic, and

[0022] (b) an effective stabilizing amount of one or more compoundsselected from the group consisting of durable hydroxyphenylbenzotriazole and tris-aryl-s-triazine UV absorbers.

[0023] The instant invention also pertains to a method of protectingcontents from the deleterious effects of ultraviolet radiation whichcomprises storage in the clear or lightly colored containers or films ofthe instant invention.

[0024] Where the plastic of component (a) is lightly colored it iscolored with pigments and/or dyes. Plastic containers and films madetherefrom transmit significant portions of radiation of the ultravioletregion, i.e. about 280 to about 400 nm. Ultraviolet absorbers (UVA's)that are red-shifted absorb radiation towards the 400 nm region of thespectrum more efficiently than UVA's that are not red-shifted. Many ofthe present benzotriazloes and s-triazines, in addition to being highlydurable, are also red-shifted.

[0025] The clear or lightly colored plastic of component (a) contains anupper limit of about 5% pigments and/or dyes by weight, in total, basedon the weight of the plastic. Preferably, the plastic of component (a)contains an upper limit of about 2% by weight pigments and/or dyes basedon the weight of the plastic. Most preferably the upper limit ofpigments and/or dyes in the plastic is about 1% by weight.

[0026] The UV absorbers of component (b) exhibit excellent compatibilitywith the plastic containers or films of this invention. Further, theyadd little or no color to finished plastic containers or films.

[0027] The contents to be protected by the compositions and methods ofthe instant invention include foodstuffs such as fruit juices, softdrinks, beer, wines, food products and dairy products, and personal careproducts, cosmetics, shampoos, vitamins, pharmaceuticals, inks, dyes andpigments.

[0028] The plastic containers and films are rigid or flexible mono-and/or multi-layered packaging materials. The containers and films maybe formed from polyesters, polyolefins, polyolefin copolymers such asethylene-vinyl acetate, polystyrene, poly(vinyl chloride),poly(vinylidene chloride), polyamides, cellulosics, polycarbonates,ethylene-vinyl alcohol, poly(vinyl alcohol), styrene-acrylonitrile andionomers and mixtures or multi-layers of these polymers.

[0029] Typical multi-layer constructions have two or more layerlaminates, manufactured either by thermoforming, or extrusion ofmulti-layer flexible films, or extrusion of bottle “preforms” or“parissons” followed by subsequent blow molding of the preforms intobottles.

[0030] For both films and rigid packaging (bottles), typically theexterior layer, and innermost layer contacting the contents, arecomposed of polyesters such as PET or PEN [poly(ethylene naphthalate)],polypropylene, or polyethylene such as HDPE. The middle layers, oftencalled ‘barrier’ or ‘adhesive’ or ‘tie’ layers, are composed of one ormore combinations of either PET, PEN, carboxylated polyethylene ionomersuch as Surlyn®, vinyl alcohol homopolymers or copolymers such aspoly(vinyl alcohol), partially hydrolyzed poly(vinyl acetate),poly(ethylene-co-vinyl alcohol) such as EVOH or EVAL, nylons orpolyamides such as Selar® (DuPont) or polyamides based onmetaxylenediamine (sometimes called nylon MXD-6), or polyvinylidenechloride (PVDC), or polyurethanes. For packaging of meats andvegetables, where a controlled rate of ‘respiration’ or oxygen andmoisture transport is desired, polystyrenes and cellulosics are used asa packaging component.

[0031] Optionally, the stabilizers of component (b) and optional furtheradditives can be incorporated intocoatings which are applied to theouter surface of e.g. rigid containers. Examples of exterior coatingsinclude PVDC, or epoxies (such as Bairocace® technology and polyolefinsused as “shrink wrap.”

[0032] The containers and films are primarily polyesters such aspoly(ethylene terephthalate) (PET) and polyolefins such as polyethyleneor polypropylene. Preferably they comprise PET or HDPE. Where thepackaging material is a multi-layer system, layers of any suitableplastic may be employed.

[0033] The polyesters which may be used in the compositions of thisinvention include linear, thermoplastic, crystalline or amorphouspolyesters produced by conventional polymerization techniques from oneor more diols and one or more dicarboxylic acids. The polyestersnormally are molding grade and have an inherent viscosity (I.V.) ofabout 0.4 to about 1.2. The preferred polyesters comprise at least about50 mole percent terephthalic acid residues and at least about 50 molepercent ethylene glycol and/or 1,4-cyclohexanedimethanol residues.Particularly preferred polyesters are those containing from about 75 to100 mole percent terephthalic acid residues and from about 75 to 100mole percent ethylene glycol residues.

[0034] The diol components of the described polyesters may be selectedfrom ethylene glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol,1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol,1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,X,8-bis(hydroxymethyl)-tricyclo-[5.2.1.0]-decane wherein X represents 3,4, or 5; and diols containing one or more oxygen atoms in the chaine.g., diethylene glycol, triethylene glycol, dipropylene glycol,tripropylene glycol and the like. In general, these diols contain 2 to18, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be employedin their cis or trans configuration or as mixtures of both forms.

[0035] The acid components (aliphatic, alicyclic, or aromaticdicarboxylic acids) of the linear polyester are selected, for example,from terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylicacid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid,adipic acid, sebacic acid, 1,12-dodecanedioic acid,2,6-naphthalene-dicarboxylic acid and the like. In the polymerpreparation, it is often preferable to use a functional acid derivativethereof such as the dimethyl, diethyl, or dipropyl ester of thedicarboxylic acid. The anhydrides or acid halides of these acids alsomay be employed where practical.

[0036] The linear polyesters may be prepared according to procedureswell known in the art. For example, a mixture of one or moredicarboxylic acids, preferably aromatic dicarboxylic acids, or esterforming derivatives thereof, and one or more diols may be heated in thepresence of esterification and/or poly-esterification catalysts attemperatures in the range of 150° to 300° C. and pressures ofatmospheric to 0.2 mm Hg. Normally, the dicarboxylic acid or derivativethereof is esterified or transesterified with the diol(s) at atmosphericpressure and at a temperature at the lower end of the specified range.Polycondensation then is effected by increasing the temperature andlowering the pressure while excess diol is removed from the mixture.Solid state polymerization may be employed to achieve final polymer I.V.in a useful range for films and molded containers.

[0037] The novel polyester compositions provided by this invention areuseful in the manufacture of containers or packages for comestibles suchas beverages and food. By the use of known heat-setting techniques,certain of the polyesters are, in terms of color, I.V. and heatdistortion, stable at temperatures up to about 100° C. Such stabilitycharacteristics are referred to herein as “hot-fill” stability. Articlesmolded from these polyesters exhibit good thin-wall rigidity, excellentclarity and good barrier properties with respect to moisture andatmospheric gases, particularly carbon dioxide and oxygen.

[0038] Rigid containers may be manufactured by known mechanicalprocesses:

[0039] a) Single-stage blow molding such as performed on Nissei, Aoki,or Uniloy machines,

[0040] b) Two-stage, injection molding of pre-forms such as on Netstalor Husky machines, and pre-forms converted to bottles by blow molding(e.g., on Sidel, Corpoplast and Krones machines),

[0041] c) Integrated blow molding of pre-forms to bottles, such asprocesses conducted on Sipa, Krupp Kautex, or Husky ISB machines, and

[0042] d) Stretch blow molding (SBM) of pre-forms to bottles.

[0043] The pre-forms may be mono-layer or multi-layer in construction.The bottles may optionally be post-treated to alter the inner wallproperties. Bottles may optionally be surface treated on the exteriorsuch as by application of surface coatings. UV absorbers and other knownstabilizers may be present in such added surface coatings.

[0044] The linear polyesters most preferred for use in articles having“hot-fill” stability comprise poly(ethylene terephthalate),poly(ethylene terephthalate) wherein up to 5 mole percent of theethylene glycol residues have been replaced with residues derived from1,4-cyclohexanedimethanol and poly(ethylene2,6-naphthalenedicarboxylate), wherein the polyesters have beensufficiently heat set and oriented by methods well known in the art togive a desired degree of crystallinity. By definition, a polymer is“hot-fill” stable at a prescribed temperature when less than 2% changein volume of a container manufactured therefrom occurs upon filling thesame with a liquid at the temperature. For the manufacture ofblow-molded beverage bottles, the most preferred polyesters have an I.V.of 0.65 to 0.85, and a Tg of >70° C., and film sections cut from thebottle have a Water Vapor Transmission Rate of 1.5 to 2.5 g mils/100in.²−24 hours, a Carbon Dioxide Permeability of 20 to 30 cc. mils/100in.²−24 hours -atm., and an Oxygen Permeability of 4 to 8 cc. mils/100in.²−24 hours -atm. The Tg is determined by Differential ScanningCalorimetry at a scan rate of 20 Centigrade Degrees/min., the OxygenPermeability by the standard operating procedure of a MOCON OXTRAN 100instrument of Modern Controls, Inc., of Elk Riber, Minn., and the CarbonDioxide Permeability by the standard operating procedure of a MOCONPERMATRAN C II, also of Modern Controls.

[0045] Examples for Polyolefins are:

[0046] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbomene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene ODPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

[0047] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0048] i) radical polymerization (normally under high pressure and atelevated temperature).

[0049] ii) catalytic polymerization using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerization medium. The catalysts can be used by themselves inthe polymerization or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0050] 2. Mixtures of the polymers mentioned under 1.), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0051] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylenelbutadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as texpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbomene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0052] Preferred polyolefins are polyethylene or polypropylene and theircopolymers with mono- and diolefins.

[0053] Particularly, the benzotriazoles of the methods of the instantinvention are of formula (I), (II) or (III)

[0054] wherein

[0055] G₁ and G₁′ are independently hydrogen or halogen,

[0056] G₂ and G₂′ are independently halogen, nitro, cyano,perfluoroalkyl of 1 to 12 carbon atoms, —COOG₃, —P(O)(C₆H₅)₂, —CO—G₃,—CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃, E₃SO— or E₃SO₂—; or G₂′ is alsohydrogen,

[0057] G₃is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms,

[0058] E₁ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1to 24 carbon atoms substituted by one or two hydroxy groups,

[0059] when E₁ is phenylalkyl of 7 to 15 carbon atoms or phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms, G₂ may also be hydrogen,

[0060] E₂ and E₂′ are independently straight or branched alkyl chain of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted onthe phenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E₂ andE₂′ are independently said alkyl of 1 to 24 carbon atoms or said alkenylof 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁, —OE₄,—NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylor said alkenyl interrupted by one or more —O—, —NH— or —NE4— groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, —OE₄ or —NH₂ groups or mixtures thereof;

[0061] n is 1 or 2,

[0062] when n is 1, E₅ is OE₆ or NE₇E₈, or

[0063] E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁, or straight or branchedchain C₁-C₂₄ alkyl which is interrupted by —O—, —S— or —NE₁₁ and whichcan be unsubstituted or substituted by —OH or —OCO—E₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl,

[0064] E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which isunsubstituted or substituted by one or more OH, OE₄ or NH₂ groups, or—OE₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 andE₂₁ is alkyl of 1 to 12 carbon atoms,

[0065] E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring,

[0066] E₅ is —X—(Z)_(p)—Y—E₁₅

[0067] wherein

[0068] X is —O— or —N(E₁₆)—,

[0069] Y is —O— or —N(E₁₇)—,

[0070] Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butenylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

[0071] m is zero, 1 or 2,

[0072] p is 1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively,

[0073] E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E,₁₇)—, formstogether with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen ormethyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₅-alkyl or a group of the formula

[0074] wherein the symbols E₁, G₂, X, Z, m and p have the meaningsdefined above, and E₁₆, and E₁₇ independently of one another arehydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms,or is cyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the casewhere Z is ethylene, also forms ethylene,

[0075] when n is 2, one of G₂ is also hydrogen, E₅ is one of divalentradicals —O—E₉—O— or —N(E₁₁)—E₁₀—N(E₁₁)—,

[0076] E₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene,cyclohexylene, straight or branched chain C₄-C₁₀alkylene which isinterrupted by —O— or by —CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—,

[0077] E₁₀ being straight or branched chain C₂-C₁₂alkylene which may beinterrupted by —O—, cyclohexylene, or

[0078] or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazinering,

[0079] E₁₄ is straight or branched chain C₂-C₈alkylene, straight orbranched chain C₄-C₁₀alkylene which is interrupted by —O—,cycloalkylene, arylene or

[0080] where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18carbon atoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene,

[0081] E₁₁ is hydrogen, straight or branched chain C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl, C₆-C₁₄arylor C₇-C₁₅aralkyl,

[0082] E₁₂ is straight or branched chain C₁-C₁₈alkyl, straight orbranched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl, C₆-C₁₆aryl orC₇-C₁₅aralkyl,

[0083] E₁₃ is H, straight chain or branched C₁-C₁₈alkyl which issubstituted by —PO(OE₁₂)₂, phenyl which is unsubstituted or substitutedby OH, C₇-C₁₅aralkyl or —CH₂OE₁₂,

[0084] E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkyl substituted by alkoxycarbonyl of 2 to 9 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, and

[0085] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylyleneor cycloalkylidene; and

[0086] with the proviso that formula (I) does not represent5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole or2-(2-hydroxy-3,5-di-α-cumyl)-2H-benzotriazole.

[0087] More particularly, the compound of formula (I) is

[0088] wherein

[0089] G₁ is hydrogen,

[0090] G₂ is hydrogen, cyano, chloro, fluoro, CF₃—, —CO—G₃, E₃SO— orE₃SO₂—,

[0091] G₃ is straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms,

[0092] E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenylor said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1to 4 carbon atoms,

[0093] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂₀ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixturesthereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH— or —NE₄— groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —OE₄ or —NH₂ groups or mixturesthereof;

[0094] E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one or two alkyl of 1 to 4carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where theperfluoroalkyl moiety is of 6 to 16 carbon atoms;

[0095] or is a compound of formula (I)

[0096] wherein,

[0097] G₁ is hydrogen,

[0098] G₂ is chloro, fluoro, CF₃—, F₃SO— or E₃SO₂—,

[0099] E₁ is hydrogen or straight or branched alkyl of 1 to 24 carbonatoms,

[0100] E₂ is as defined above, and

[0101] E₃ is straight or branched chain alkyl of 1 to 7 carbon atoms;and

[0102] with the proviso that formula (I) does not represent5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole or2-(2-hydroxy-3,5-di-α-cumyl)-2H-benzotriazole.

[0103] Another preferred embodiment is where the benzotriazole is offormula (IIA)

[0104] wherein

[0105] G₁ is hydrogen,

[0106] G₂ is CF₃— or fluoro,

[0107] E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms,

[0108] when E₁ is phenylalkyl of 7 to 15 carbon atoms, G₂ may also behydrogen,

[0109] E₅ is —OE₆ or —NE₇E₈, or

[0110] E₅ is

[0111] —X—(Z)_(p)—Y—E₁₅

[0112] wherein

[0113] X is —O— or —N(E₁₆)—,

[0114] Y is —O— or —N(E₁₇)—,

[0115] Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butenylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

[0116] m is 0, 1, 2 or 3,

[0117] p is 1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively,

[0118] E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, formstogether with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen ormethyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula

[0119] Still another preferred embodiment is a benzotriazole of formula(IIIA)

[0120] wherein

[0121] G₂ is CF₃,

[0122] G₂ is hydrogen or CF₃,

[0123] E₂ and E₂′ are independently straight or branched alkyl chain of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted onthe phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

[0124] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylyleneor cycloalkylidene.

[0125] In a more preferred embodiment, the benzotriazole is of formula(I)

[0126] wherein

[0127] G₁ is hydrogen,

[0128] G₂ is CF₃—,

[0129] E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenylor said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1to 4 carbon atoms,

[0130] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —NH₂ or —NHCOE₁₁, or mixtures thereof, or said alkyl orsaid alkenyl interrupted by one or more —O— and which can beunsubstituted or substituted by one or more —OH,

[0131] or is a compound of formula (I) wherein,

[0132] G₁ is hydrogen,

[0133] G₂ is CF₃—,

[0134] E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms, and

[0135] E₂ is as defined above.

[0136] In another preferred embodiment, the benzotriazole is of formula(IIA)

[0137] wherein

[0138] G₁ is hydrogen,

[0139] G₂ is CF₃—,

[0140] E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms,

[0141] E₅ is —OE₆ or —NE₇E₈ where

[0142] E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which isunsubstituted or substituted by one or more OH groups, or —OE₆ is—(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ isalkyl of 1 to 12 carbon atoms, and

[0143] E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring.

[0144] In an especially preferred embodiment, the benzotriazole is offormula (IIIA)

[0145] wherein

[0146] G₂ is CF₃,

[0147] G₂, is hydrogen or CF₃,

[0148] E₂ and F₂′ are independently straight or branched alkyl chain of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted onthe phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

[0149] L is methylene.

[0150] Preferably, the benzotriazole is a compound which is

[0151] (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0152] (b)5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

[0153] (c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

[0154] (d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)4-tert-octylphenol];

[0155] (e)methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-butyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];

[0156] (f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid;

[0157] (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0158] (h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butylhydroxy-hydrocinnamate;

[0159] (i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

[0160] (j)5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0161] (k)5-octylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0162] (l)5-dodecylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0163] (m)5-octylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

[0164] (n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

[0165] (o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;

[0166] (p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzo-triazole;

[0167] (q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzo-triazole;

[0168] (r)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0169] (s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0170] (t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

[0171] (u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzo-triazole;

[0172] (v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethylphenyl]-2H-benzo-triazole;

[0173] (w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

[0174] (x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0175] (y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0176] (z)5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0177] (aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0178] (bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

[0179] (cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0180] (dd)5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0181] (ee)5-chloro2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0182] (ff) isooctyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl4-hydroxyhydrocinnamate;and

[0183] (gg) 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

[0184] Most preferably, the benzotriazoles of special interest are

[0185] (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0186] (b)5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

[0187] (c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

[0188] (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0189] (j)5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0190] (n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

[0191] (s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0192] (x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0193] (aa)5-butylsulfonyl-2-(2-hydroxy-3,54-di-tert-butylphenyl)-2H-benzotriazole;and

[0194] (cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

[0195] The durable tris-aryl-s-triazines of the instant invention aretypical commercial s-triazine UV absorbers based on4,6-bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-s-triazine such asTinuvin® 400, Ciba Specialty Chemicals Corp., and Cyasorb® 1164, CytecCorporation, or they are red-shifted s-triazines as disclosed forexample in U.S. Pat. Nos. 5,556,973 and 5,354,794, or they are highmolar extinction s-triazines as disclosed in copending ApplicationSerial No. 09/383,163.

[0196] The s-triazine UV absorbers of component (b) are of formula (IV),(), (VI), (VII), (VIII) or (IX)

[0197] wherein

[0198] X and Y are independently phenyl, naphthyl, or said phenyl orsaid naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms,by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or bymixtures thereof; or X and Y are independently Z₁ or Z₂;

[0199] R₁ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, halogen, —SR₃, —SOR₃ or —SO₂R₃; or said alkyl, saidcycloalkyl or said phenylalkyl substituted by one to three halogen, —R₄,—OR₅, —N(R₅)₂, —COR₅, —COOR₅, —OCOR₅, —CN, —NO₂, —SR₅, —SOR₅, —SO₂R₅ or—P(O)(OR₅)₂, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl,piperazinyl or N-methylpiperidinyl groups or combinations thereof; orsaid alkyl or said cycloalkyl interrupted by one to four phenylene, —O—,—NR₅—, —CONR₅—, —COO—, —OCO— or —CO groups or combinations thereof; orsaid alkyl or said cycloalkyl both substituted and interrupted bycombinations of the groups mentioned above;

[0200] R₃ is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one ortwo alkyl of 1 to 4 carbon atoms;

[0201] R₄ is aryl of 6 to 10 carbon atoms or said aryl substituted byone to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbonatoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkylsubstituted on the phenyl ring by one to three halogen, alkyl of 1 to 8carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; orstraight or branched chain alkenyl of 2 to 18 carbon atoms;

[0202] R₅ is defined as is R₄; or R₅ is also hydrogen or straight orbranched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbonatoms; or R₅ is a group for formula

[0203] T is hydrogen, oxyl, hydroxyl, —OT₁, alkyl of 1 to 24 carbonatoms, said alkyl substituted by one to three hydroxy; benzyl oralkanoyl of 2 to 18 carbon atoms;

[0204] T₁ is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated orunsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms oraryl of 6 o 10 carbon atoms or said aryl substituted by one to threealkyl of 1 to 4 carbon atoms;

[0205] R₂ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl orsaid cycloalkyl substitute by one to four halogen, epoxy, glycidyloxy,furyloxy, —R₄, —OR₅, —N(₅)₂, —CON(R₅)₂, —COR₅, —COOR₅, —OCOR₅,—OCOC(R₅)═C(R₅)₂, —C(R₅)═CCOOR₅, —CN, —NCO, or

[0206] or combinations thereof; or said alkyl or said cycloalkylinterrupted by one to four epoxy, —O—, —N₅—, —CONR₅—, —COO—, —OCO—,—CO—, —C(R₅)═C(R₅)COO—, —OCOC(R₅)═C (R₅)—, —C(R₅)═C(R₅)—, phenylene orphenylene-G-phenylene in which G is —O—, —S—, —SO₂—, —CH₂— or —C(CH₃)₂—or combinations thereof, or said alkyl or said cycloalkyl bothsubstituted and interrupted by combinations of the groups mentionedabove; or R₂ is —SO₂R₃ or —COR₆;

[0207] R₆ is straight or branched chain alkyl of 1 to 18 carbon atoms,straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy,alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms,—R₇COOH or —NH—R₈—NCO;

[0208] R₇ is alkylene of 2 to 14 carbon atoms or phenylene;

[0209] R₈ is alkylene of 2 to 24 carbon atoms, phenylene, tolylene,diphenylmethane or a group

[0210] R₁′ and R₁″ are the same or different and are as defined for R₁;

[0211] R₂′ and R₂″ are the same or different and are as defined for R₂;

[0212] X, X′, Y and Y′ are the same or different and are as defined forX and Y;

[0213] t is 0 to 9;

[0214] L is straight or branched alkylene of 1 to 12 carbon atoms,cycloalkylene of 5 to 12 carbon atoms or alkylene substituted orinterrupted by cyclohexylene or phenylene; or L is benzylidene; or L is—S—, —S—S—, —S—E—S—, —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—,—CH₂—NH—E—NH—CH₂— or

[0215] E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5to 12 carbon atoms;

[0216] n is 2, 3 or 4;

[0217] when n is 2; Q is straight or branched alkylene of 2 to 16 carbonatoms; or said alkylene substituted by one to three hydroxy groups; orsaid alkylene interrupted by one to three —CH═CH— or —O—; or saidalkylene both substituted and interrupted by combinations of the groupsmentioned above; or Q is xylylene or a group —CONH—R₈—NHCO—,—CH₂CH(OH)CH₂O—R₉—OCH₂CH(OH)CH₂—, —CO—R₁₀—CO—, or—(CH₂)_(m)—COO—R₁₁—OOC—(CH₂)_(m)—, where m is 1 to 3; or Q is

[0218] R₉ is alkylene of 2 to 50 carbon atoms; or said alkyleneinterrupted by one to ten —O—, phenylene or a group-phenylene-G-phenylene in which G is —O—, —S—, —SO₂—, —CH₂— or—C(CH₃)₂—;

[0219] R₁₀ is alkylene of 2 to 10 carbon atoms, or said alkyleneinterrupted by one to four —O—, —S— or —CH═CH—; or R₁₀ is arylene of 6to 12 carbon atoms;

[0220] R₁₁ is alkylene of 2 to 20 carbon atoms or said alkyleneinterrupted by one to eight —O—;

[0221] when n is 3, Q is a group —[(CH₂)_(m)COO]₃—R₁₂ where m is 1 to 3,and R₁₂ is an alkanetriyl of 3 to 12 carbon atoms;

[0222] when n is 4, Q is a group —[(CH₂)_(m)COO]₄—R₁₃ where m is 1 to 3,and R₁₄ is an alkanetetrayl of 4 to 12 carbon atoms;

[0223] Z₁ is a group of formula

[0224] Z₂ is a group of formula

[0225] where

[0226] r₁ and r₂ are independently of each other 0 or 1;

[0227] R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ areindependent of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy,acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms,alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl; or R₁₇ and R₁₈or R₂₂ and R₂₃ together with the phenyl radical to which they areattached are a cyclic radical interrupted by one to three —O— or —NR₅—;

[0228] with the proviso that the compound of formula (IV) is not4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s -triazine.

[0229] Preferably, the invention pertains to compounds of formula (IV)where X and Y are the same or different and are phenyl or said phenylsubstituted by one to three alkyl of 1 to 6 carbon atoms, halogen,hydroxy or alkoxy of 1 to 12 carbon atoms; or X and Y are Z₁ or Z₂;

[0230] R₁ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms or halogen;

[0231] R₂ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl orsaid cycloalkyl substituted by one to three —R₄, —OR₅, —COOR₅, —OCOR₅ orcombinations thereof; or said alkyl or cycloalkyl interrupted by one tothree epoxy, —O—, —COO—, —OCO— or —CO—;

[0232] R₄ is aryl of 6 to 10 carbon atoms or said aryl substituted byone to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbonatoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkylsubstituted on the phenyl ring by one to three halogen, alkyl of 1 to 8carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;

[0233] R₅ is defined as is R₄; or R₅ is also hydrogen or straight orbranched chain alkyl of 1 to 24 carbon atoms;

[0234] Z₁ is a group of formula

[0235] Z₂ is a group of formula

[0236] where r₁ and r₂ are each 1; and

[0237] R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ areindependently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy,acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, oralkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl;

[0238] with the proviso that the compound of formula (IV) is not4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.

[0239] Preferably, the s-triazine UV absorber is also of formula (V)where

[0240] X is phenyl, naphthyl or said phenyl or said naphthyl substitutedby one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy orby alkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X is Z₁.

[0241] Preferably, the s-triazine UV absorber is also of formula (VI).

[0242] Preferably, the s-triazine UV absorber is also of formula (IX)where

[0243] X and Y are independently phenyl or said phenyl substituted byone to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or byalkoxy of 1 to 6 carbon atoms or by mixtures thereof; or X and Y areindependently Z₁ or Z₂; and

[0244] L is straight or branched alkylene of 1 to 12 carbon atoms,cycloalkylene of 5 to 12 carbon atoms or alkylene substituted orinterrupted by cyclohexylene or phenylene.

[0245] Most preferably, the instant s-triazine UV absorber is of formula(IV) where X and Y are the same or different and are phenyl or saidphenyl substituted by one to three alkyl of 1 to 6 carbon atoms; Z₁ orZ₂;

[0246] R₁ is hydrogen or phenylalkyl of 7 to 15 carbon atoms;

[0247] R₂is hydrogen, straight or branched chain alkyl of 1 to 18 carbonatoms; or said alkyl substituted by one to three —R₄, —OR₅ or mixturesthereof; or said alkyl interrupted by one to eight —O— or —COO—;

[0248] R₄ is aryl of 6 to 10 carbon atoms;

[0249] R₅ is hydrogen;

[0250] Z₁ is a group of formula

[0251] Z₂ is a group of formula

[0252] where

[0253] r₁ and r₂ are each 1; and

[0254] R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are eachhydrogen;

[0255] with the proviso that the compound of formula (IV) is not4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s -triazine.

[0256] Preferably, the s-triazine UV absorber of this invention is acompound which is

[0257] methylene bridged dimer mixture bridged in the 3:5′, 5:5′ and3:3′ position in a 5:4:1 ratio

[0258] The names of the instant compounds illustrated in the structuresgiven above as listed below as indicated.

[0259] (1)2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;

[0260] (2)2-phenyl-4-[2-hydroxy4(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;

[0261] (3)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine;

[0262] (4)2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine;

[0263] (5)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine;(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups)

[0264] (6)methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy4-(3-butyloxy-2-hydroxy-propoxy)phenyl]-s-triazine}, methylene bridged dimer mixture bridged inthe 3:5′, 5:5′ and 3:3′ positions in a 5:4:1 ratio;

[0265] (7)2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;

[0266] (8)2,4-bis(2,4dimethylphenyl)-6-(2-hydroxy4-hexyloxy-5-α-cumylphenyl)-s-triazine;

[0267] (9)2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,CYASORB® 1164, Cytec;

[0268] (10)2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine;or

[0269] (11)2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine.

[0270] Preferably, the s-triazine UV absorber of component (b) is

[0271] (1)2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;

[0272] (5)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine;(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups) or

[0273] (7)2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine.

[0274] The effective stabilizing amount of the compound or compounds ofcomponent (b) is about 0.1 to about 20% by weight based on the weight ofthe plastic container or film composition.

[0275] A preferred embodiment of the present invention are wheremixtures of stabilizers of component (b) are employed, for example amixture of at least one benzotriazole and at least one s-triazine or amixture of two or more benzotriazoles or two or more s-triazines. The UVabsorbers of component (b) are all highly durable, but have different UVlight absorbing characteristics depending on their substitution pattern.By selection of particular combinations of UV absorbers, one mayoptimize the UV absorbing characteristics and the color of thecompositions of this invention.

[0276] Another preferred embodiment of the present invention is where abenzotriazole UV absorber not of the class described herein is employedin addition to the compound or compounds of component (b).

[0277] The instant plastic container or film stabilized by a compound orcompounds of component (b) may also optionally contain from about 0.01to about 10% by weight; preferably from about 0.025 to about 5% byweight, and most preferably from about 0.1 to about 3% by weight ofadditional coadditives such as antioxidants, other UV absorbers,hindered amines, phosphites or phosphonites, hydroxylamines, nitrones,benzofuran-2-ones, thiosynergists, polyamide stabilizers, metalstearates, nucleating agents, fillers, reinforcing agents, lubricants,emulsifiers, dyes, pigments, optical brighteners, flame retardants,antistatic agents, blowing agents and the like.

[0278] The stabilizers of the instant invention may readily beincorporated into the present container or film compositions byconventional techniques, at any convenient stage prior to themanufacture of articles therefrom. For example, the stabilizer may bemixed with the polymer in dry powder form, or a suspension or emulsionof the stabilizer may be mixed with a solution, suspension, or emulsionof the polymer. The resulting stabilized compositions of the inventionmay optionally also contain from about 0.01 to about 10%, preferablyfrom about 0.025 to about. 5%, and especially from about 0.1 to about 3%by weight of various conventional stabilizer coadditives, such as thematerials listed below, or mixtures thereof.

[0279] 1. Antioxidants

[0280] 1.1. Alkylated monophenols, for example,

[0281] 2,6-di-tert-butyl-4-methylphenol

[0282] 2-tert-butyl-4,6-dimethylphenol

[0283] 2,6-di-tert-butyl-4-ethylphenol

[0284] 2,6-di-tert-butyl-4-n-butylphenol

[0285] 2,6-di-tert-butyl-4-i-butylphenol

[0286] 2,6-di-cyclopentyl-4-methylphenol

[0287] 2-(α-methylcyclohexyl)-4,6-dimethylphenol

[0288] 2,6-di-octadecyl-4-methylphenol

[0289] 2,4,6-tri-cyclohexylphenol

[0290] 2,6-di-tert-butyl-4-methoxymethylphenol

[0291] 1.2. Alkylated hydroquinones, for example,

[0292] 2,6-di-tert-butyl-4-methoxyphenol

[0293] 2,5-di-tert-butyl-hydroquinone

[0294] 2,5-di-tert-amyl-hydroquinone

[0295] 2,6-diphenyl-4-octadecyloxyphenol

[0296] 1.3. Hydroxylated thiodiphenyl ethers, for example,

[0297] 2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

[0298] 2,2′-thio-bis-(4-octylphenol)

[0299] 4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

[0300] 4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

[0301] 1.4. Alkylidene-bisphenols, for example,

[0302] 2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

[0303] 2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

[0304] 2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

[0305] 2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

[0306] 2,2′-methylene-bis-(6-nonyl-4-methylphenol)

[0307] 2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

[0308] 2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

[0309] b 2,2′-methylene-bis-(4,6-di-tert-butylphenol)

[0310] 2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

[0311] 2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

[0312] 4,4′-methylene-bis-(2,6-di-tert-butylphenol)

[0313] 4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

[0314] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0315] 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

[0316] 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0317]1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)3-n-dodecylmercaptobutane

[0318] ethyleneglycolbis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

[0319] di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

[0320]di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)6-tert-butyl-4-methylphenyl]terephthalate.

[0321] 1.5. Benzyl compounds, for example,

[0322]1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

[0323] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

[0324] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctylester

[0325] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

[0326] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

[0327] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

[0328] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecylester

[0329] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylester, calcium-salt

[0330] 1.6. Acylaminophenols, for example,

[0331] 4-hydroxy-lauric acid anilide

[0332] 4-hydroxy-stearic acid anilide

[0333]2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

[0334] octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

[0335] 1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example, methanoldiethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

[0336] 1.8. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydricor polyhydric alcohols, for example, methanol diethylene glycoloctadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentylglycol tris-hydroxyethyl isocyanurate thiodiethylene glycoldi-hydroxyethyl oxalic acid diamide triethanolamine triisopropanolamine

[0337] 1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid for example,

[0338]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

[0339]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

[0340] N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

[0341] 2. UV absorbers and light stabilizers

[0342] 2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

[0343] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0344] 2.3. Esters of optionally substituted benzoic acids for example,phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

[0345] 2.4. Acrylates and malonates, for example,α-cyano-β,β-diphenylacrylic acid ethyl ester or isooctyl ester,α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline, Sanduvore® PR25,dimethyl p-methoxybenzylidenemalonate (CAS# 7443-25-6), and Sanduvor®PR31, di-(1,2,2,6,6-pentamethylpiperidin-4-yl)p-methoxybenzylidenemalonate (CAS #147783-69-5).

[0346] 2.5. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

[0347] 2.6. Sterically hindered amines substituted on the N-atom by ahydroxy-substituted alkoxy group, for example compounds disclosed incopending application Serial No. 09/257,711, and whose relevant partsare also incorporated herein by reference, such as1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine,1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethyl-piperidine,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)succinate,bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)glutarate and2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine.

[0348] 2.7. Oxalic acid diamides, for example,4,4′-di-octyloxy-oxanilide, 2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide, 2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

[0349] 2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy4(2-hydroxy-ethoxy)phenyl]-6-(4chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

[0350] 3. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-iso-decylpentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite,tetrakis-(2,4-di-tert-butylphenyl)-4,4′-diphenylylenediphosphonite.

[0351] 4. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

[0352] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxyl-amine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0353] 6. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

[0354] 7. Amine oxides, for example amine oxide derivatives as disclosedin U.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

[0355] 8. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0356] 9. Basic co-stabilizers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0357] 10. Nucleating agents, for example, 4-tert-butyl-benzoic acid,adipic acid, diphenylacetic acid.

[0358] 11. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite.

[0359] 12. Other additives, for example, plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearyl thiodipropionate.

[0360] 13. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. Nos. 4,325,863, 4,338,244 or 5,175,312, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4,2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl4-piva-loyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0361] The co-stabilizers, with the exception of the benzofuranoneslisted under 13., are added for example in concentrations of about 0.01to about 10%, relative to the total weight of the material to bestabilized.

[0362] Further preferred compositions comprise, in addition tocomponents (a) and (b) further additives, in particular phenolicantioxidants, light stabilizers or processing stabilizers.

[0363] Particularly preferred additives are phenolic antioxidants,sterically hindered amines, phosphites and phosphonites, UV absorbersand peroxide-destroying compounds.

[0364] Additional additives (stabilizers) which are also particularlypreferred are benzofuran-2-ones, such as described, for example, in U.S.Pat. Nos. 4,325,863, 4,338,244 or 5,175,312.

[0365] The phenolic antioxidant of particular interest is selected fromthe group consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl4-tert-butyl-3-hydroxybenzyl)isocyanurate,1,1,3,-tris(2-methyl4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide,N,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide,2,4-bis(octylthio-methyl)-6-methylphenol, and2,4-bis(octylthiomethyl)-6-tert-butylphenol.

[0366] A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol,2,2′-ethylidene-bis(4,6-di-tert-butylphenol),2,4-bis(octylthiomethyl)-6-methylphenol or2,4-bis(octylthiomethyl)-6-tert-butyl-phenol.

[0367] The hindered amine compound of particular interest is selectedfrom the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)-butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethyl-piperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetraimethylpiperidine) and1,2-dibromoethane,tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl-β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethyl]1,2,3,4-butanetetracarboxylate,octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-dodecylsuccinimide,1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin -4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,2-(2-hydroxyethyl)amino-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butyl-amino]-s-triazine,1,2-bis(3,3,5,5-tetramethylpiperazin-2-on-1-yl)ethane,1,3,5-tris{N-cyclohexyl-N-[2-(3,3,5,5-tetramethylpiperazin-2-on-1-yl)ethyl]amino}-s-triazine,1,3,5-tris{N-cyclohexyl-N-[2-(3,3,4,5,5-pentaamethylpiperazin-2-on-1-yl)ethyl]amino}-s-triazine,reaction of 2-4 equivalents of2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith 1 equivalent of N,N′-bis(3-aminopropyl)ethylene-diamine,bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-etramethylpiperidinayl-4-yl]sebacate, mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinyl-4-yl-]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidinayl-4-yl]adipate,4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidineand4-octadecyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

[0368] A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidinyl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,2-(2-hydroxyethyl)amino-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,1,2-bis(3,3,5,5-tetramethylpiperazin-2-on-1-yl)ethane,1,3,5-tris{N-cyclohexyl-N-[2-(3,3,5,5-tetramethylpiperidin-zin-2-on-1-yl)ethyl]amino}-s-triazine,1,3,5-tris{N-cyclohexyl-N-[2-(3,3,4,5,5-pentamethyl-piperazin-2-on-1-yl)ethyl]amino}-s-triazine,reaction of 2-4 equivalents of2,4-bis[(1-cyclohexyl-oxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazinewith 1 equivalent of N,N′-bis(3-aminopropyl)ethylenediamine,bis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidinyl-4-yl]sebacate,mixture ofbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetraethyl-piperidin-4-yl]glutarate andbis[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]adipate,4-hydroxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine or4-octa-decyloxy-1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine.

[0369] The instant composition can additionally contain another UVabsorber selected from the group consisting of benzotriazoles,s-triazines, oxanilides, hydroxybenzophenones, benzoates,α-cyanoacrylates, malonates, salicylates, and benzoxazinones2,2′-p-phenylene-bis(3,1-benzoxazin-4-one), Cyasorb® 3638 (CAS#18600-59-4), Cytec Corp.

[0370] Of particular interest as optional co-additives in the presentcompositions are those selected from the classes of known benzotriazoleUV absorbers and hindered amine compounds.

[0371] The following examples are for illustrative purposes only and arenot to be construed to limit the instant invention in any mannerwhatsoever.

[0372] The following additives are used in the working Examples:

[0373] Tinuvin® 327,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,

[0374] Chimassorb® 81, 2-hydroxy4-octyloxybenzophenone, and

[0375] Tinuvin® 928,3-α-cumyl-2-hydroxy-5-t-octylphenyl-2H-benzotriazole and

[0376] (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

[0377] Tinuvin® 327, Chimassorb 81 and Tinuvin* 928 are available fromCiba Specialty Chemicals.

EXAMPLE 1 PET Bottles

[0378] PET concentrates (10% by weight) of the UV-absorbers of Table 1are prepared using Eastapak 9921W PET, on a 27 mm twin screw extruder atan operating temperature at die of 275° C. The concentrates are letdownwith base resin to the final additive loading indicated in Table 1. PETis dried in vacuo for at least 4 hours at 240° F. prior to preformmolding. Preforms are molded on a unit cavity Arburg press using theminimum injection temperature and back pressure necessary to obtainparts free of haze an crystallinity. Bottle blow molding is conductedusing a Sidel SBO 2/3 blow molding machine, using preforms describedabove. Bottle wall thickness of 0.015-0.016 inches is achieved. TABLE 1Formulation UV Absorber weight % on resin 1 (control) none 2 (control)Tinuvin ® 327 0.3 3 (control) Chimassorb ® 81 0.3 4 UVA (a) 0.3 5 1:1mix of Tinuvin ® 928 0.3 and UVA (a)

[0379] The molded bottles represent 16-20 oz. water or soda type PETbottles and 200 mL cough syrup type PET bottles.

EXAMPLE 2 Percent Transmission

[0380] Percent transmission data is obtained for 200 mL cough syrupbottles prepared according to Example 1. Percent transmission ismeasured for bottles prepared from formulations 1 and 5 and reported inthe following table. Wavelength (nm) Formulation 1 Formulation 5 330 250 340 41 0 350 50 0 360 57 0 370 67 0 380 71 0 390 73 0

[0381] Essentially all the damaging UV light is screened with thebottles which have incorporated therein a small amount of UV absorber(a) of the present invention.

[0382] For the following Examples the exposure conditions are asfollows:

[0383] Sample are exposed under a bank of six (6) cool white fluorescentlamps (40 watts) or under a bank of six (6) UV lamps having a wavelengthof 368 nm with the test samples being twelve (12) inches (30.48 cm)below the lamps.

[0384] Dye color fade (or color change) is measured by a MacbethColorEye Spectrophotometer with a 6 inch integating sphere. Theconditions are: 10 degree observer; D65 illuminant and 8 degree viewingangle.

[0385] Initial color measurements are taken using the above parameters.The L, a and b values are calculated using the CIE system from thereflectance values. YI is calculated from the L, a and b values.Subsequent measurements are taken at specified intervals. Delta L, a, band YI values are simply the difference between the initial values andthe values at each interval. Delta (Δ) E is calculated as follows:[(ΔL)²+(Δa)²+(Δb)²]^(1/2)=Δ E

[0386] A low Δ E indicates less change in color and is highly desirable.

EXAMPLE 3 Color Stabilization of Commercial Mouthwash

[0387] The commercial mouthwash is Listerine® Tartar Control antisepticmouthwash, U.S. Pat. No. 5,891,422, which contains F & DC Blue #1(Warner-Lambert Consumer Healthcare). The color change of the mouthwashcontained in 16 oz. PET bottles prepared according to Example 1 ismeasured after exposure to fluorescent light. The bottles are filled to¾ full (500 g of mouthwash) and the lids are securely fastened. Thebottles are exposed as above. Delta E is measured for bottles preparedfrom formulations 1, 2 and 4. Formulation Δ E after 2 days 2 1.28 4 1.01

[0388] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 4 Color Stabilization of Commercial Mouthwash

[0389] The commercial mouthwash is Listerine® Tartar Control antisepticmouthwash, U.S. Pat. No. 5,891,422, which contains F & DC Blue #1(Warner-Lambert Consumer Healthcare). The color change mouthwashcontained in 16 oz. PET bottles prepared according to Example 1 ismeasured after exposure to ultraviolet (UV) light. The bottles arefilled to ¾ full (500 g of mouthwash) and the lids are securelyfastened. The bottles are exposed as above. Delta E is measured forbottles prepared from formulations 1, 2 and 4. Formulation Δ E after 1day 1 0.68 2 0.67 4 0.60

[0390] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 5 Color Stabilization of an Aqueous Dye Solution

[0391] The commercial dye is Fast Green FCF (C.I. 42053; Food Green 3),purchased from Sigma-Aldrich. The color change of the solutions in 16oz. PET bottles prepared according to Example 1 is measured afterexposure to fluorescent light. The bottles are filled to ¾ full with 500g of a 2 ppm aqueous dye solution and the lids are securely fastened.The bottles are exposed as above. Delta E is measured for bottlesprepared from formulations 1, 2 and 4. Formulation Δ E after 1 day 10.67 2 0.45 4 0.35

[0392] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 6 Color Stabilization of an Aqueous Dye Solution

[0393] The commercial dye is Fast Green FCF (C.I. 42053; Food Green 3),purchased from Sigma-Aldrich. The color change of the solutions in 16oz. PET bottles prepared according to Example 1 is measured afterexposure to ultraviolet (UV) light. The bottles are filled to ¾ fullwith 500 g of a 2 ppm aqueous dye solution and the lids are securelyfastened. The bottles are exposed as above. Delta E is measured forbottles prepared from formulations 1, 2 and 4. Formulation Δ E after 4days 1 2.34 4 2.03

[0394] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 7 Color Stabilization of a Commercial Shampoo

[0395] The commercial shampoo is Suave® Strawberry Shampoo whichcontains D&C Orange #4 (C.I. 15510) and D&C Red #33 (C.I. 17200). Thecolor change of the shampoo in 16 oz. PET bottles prepared according toExample 1 is measured after exposure to fluorescent light. The bottlesare filled to ¾ full with 500 g of the shampoo and the lids are securelyfastened. The bottles are exposed as above. Delta E is measured forbottles prepared from formulations 1, 2 and 4. Formulation Δ E after 4days 1 1.76 2 1.21 4 1.12

[0396] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 8 Color Stabilization of a Commercial Shampoo

[0397] The commercial shampoo is Suave® Strawberry Shampoo whichcontains D&C Orange #4 (C.I. 15510) and D&C Red #33 (C.I. 17200). Thecolor change of the shampoo in 16 oz. PET bottles prepared according toExample 1 is measured after exposure to ultraviolet (UV) light. Thebottles filled to ¾ full with 500 g of the shampoo and the lids aresecurely fastened. The bottles are exposed as above. Delta E is measuredfor bottles prepared from formulations 1, 2 and 4. Formulation Δ E after4 days 1 3.73 4 1.34

[0398] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 9 Color Stabilization of Commercial Mouthwash

[0399] The commercial mouthwash is Listerine® Tartar Control antisepticmouthwash, U.S. Pat. No. 5,891,422, which contains F & DC Blue #1(Warner-Lambert Consumer Healthcare). The color change of the mouthwashcontained in 200 mL bottles prepared according to Example 1 is measuredafter exposure to fluorescent light. The bottles are filled to ¾ full(140 g of mouthwash) and the lids are securely fastened. The bottles areexposed as above. Delta E is measured for bottles prepared fromformulations 1, 2, 3 and 5. Formulation Δ E after 3 days 1 0.96 2 0.73 30.56 5 0.45

[0400] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 10 Color Stabilization of Commercial Mouthwash

[0401] The commercial mouthwash is Listerine® Tartar Control antisepticmouthwash, U.S. Pat. No. 5,891,422, which contains F & DC Blue #1(Warner-Lambert Consumer Healthcare). The color change of the mouthwashcontained in 200 mL bottles prepared according to Example 1 is measureafter expose to ultraviolet (UV) light. The bottles are filled to ¾ full(140 g of mouthwash) and the lids are securely fastened. The bottles areexposed as above. Delta E is measured for bottles prepared fromformulations 1, 2, 3 and 5. Formulation Δ E after 4 days 1 0.61 3 1.52 50.36

[0402] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 11 Color Stabilization of an Aqueous Dye Solution

[0403] These commercial dye is Erioglaucine (blue dye), purchased fromSigma-Aldrich. The color change of the aqueous solution contained in 200mL bottles prepared according to Example 1 is measured after exposure toultraviolet (UV) light. The bottles are filled to ¾ full with a 2 ppmaqueous dye solution (140 g of solution) and the lids are securelyfastened. The bottles are exposed as above. Delta E is measured forbottles prepared from formulations 1, 2, 3 and 5. Formulation Δ E after1 day 1 0.15 2 0.26 3 0.33 5 0.12

[0404] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 12 Color Stabilization of a Commercial Shampoo

[0405] The commercial shampoo is Suave® Strawberry Shampoo whichcontains D&C Orange #4 (C.I. 15510) and D&C Red #33 (C.I. 17200). Thecolor change of the shampoo contained in 200 mL bottles preparedaccording to Example 1 is measured after exposure to fluorescent light.The bottles are filled to ¾ fill with the shampoo (140 g) and the lidsare securely fastened The bottles are exposed as above. Delta E ismeasured for bottles prepared from formulations 1, 2, 3 and 5.Formulation Δ E after 4 days 1 1.54 2 1.31 3 1.47 5 1.26

[0406] these data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 13 Color Stabilization of a Commercial Shampoo

[0407] These commercial shampoo is Suave® Strawberry Shampoo whichcontains D&C Orange #4 (C.I. 15510) and D&C Red #33 (C.I. 17200). Thecolor change of the shampoo contained in 200 mL bottles preparedaccording to Example 1 is measured after exposure to ultraviolet (UV)light. The bottles are filled to ¾ full with the shampoo (140 g) and thelids are securely fastened. The bottles are exposed as above. Delta E ismeasured for bottles prepared from formulations 1, 2, 3 and 5.Formulation Δ E after 2 days 1 4.47 2 0.97 3 1.57 5 0.84

[0408] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 14 Color Stabilization of an Aqueous Dye Solution

[0409] The commercial dye is Tartrazine (C.I. 19140, Acid Yellow 23),purchased from Sigma-Aldrich. The color change of the aqueous solutioncontained in 200 mL bottles prepared according to Example 1 is measuredafter exposure to fluorescent light. The bottles are filled to ¾ fullwith a 3 ppm aqueous dye solution (140 g of solution) and the lids aresecurely fastened. The bottles are exposed as above. Delta E is measuredfor bottles prepared from formulations 1, 2, 3 and 5. Formulation Δ Eafter 4 days 1 0.20 2 0.18 3 0.28 5 0.13

[0410] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional UV absorber.

EXAMPLE 15 Color Stabilization of an Aqueous Dye Solution

[0411] These commercial dye is Tartrazine (C.I. 19140, Acid Yellow 23),purchased from Sigma-Aldrich. The color change of the aqueous solutioncontained in 200 mL bottles prepared according to Example 1 is measuredafter exposure to ultraviolet (UV) light. The bottles are filled to ¾full with a 3 ppm aqueous dye solution (140 g of solution) and the lidsare securely fastened. The bottles are exposed as above. Delta E ismeasured for bottles prepared from formulations 1, 2, 3 and 5.Formulation Δ E after 1 day 1 0.84 3 0.58 5 0.50

[0412] These data indicate that PET bottles which have incorporatedtherein a UV absorber of the present invention, protects the contentsfrom unwanted discoloration far better than a conventional absorber.

EXAMPLE 16

[0413] To separate poly(ethylene terephthalate), PET, resin formulationsare added 0.5% by weight of each of the following benzotriazolestabilizers:

[0414] (ee)5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0415] (ff) isooctyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

[0416] (gg) 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0417] (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0418] (b)5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

[0419] (c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

[0420] (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0421] (j)5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;

[0422] (n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

[0423] (s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0424] (x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0425] (aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;and

[0426] (cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

[0427] Each of the stabilized resin compositions are then blow orinjection molded into a PET bottle having incorporated therein each ofthe UV absorbers. The PET bottles are especially effective at protectingthe contents therein from UV radiation, allowing a longer shelf life ofthe product.

EXAMPLE 17

[0428] To separate poly(ethylene terephthalate), PET, resin formulationsare added 0.5% by weight of each of the following s-triazinestabilizers:

[0429] (1)2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;

[0430] (2)2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;

[0431] (3)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine;

[0432] (4)2,4-bis(2-hydroxy-4-n-butyloxyphenyl)-6-(2,4-di-n-butyloxyphenyl)-s-triazine;

[0433] (5)2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine;(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups)

[0434] (6)methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxy-propoxy)phenyl]-s-triazine}, methylene bridged dimer mixture bridged inthe 3:5′, 5:5′ and 3:3′positions in a 5:4:1 ratio;

[0435] (7)2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;

[0436] (8)2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy4-hexyloxy-5-α-cumylphenyl)-s-triazine;

[0437] (9)2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,CYASORB® 1164, Cytec;

[0438] (10)2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine; and

[0439] (11)2,4,6-tris[2-hydroxy4-(3-sec-butyloxy-2-hydroxypropyloxymphenyl]-s-triazine.

[0440] Each of the stabilized resin compositions are then blow orinjection molded into a PET bottle having incorporated therein each ofthe UV absorbers. The PET bottles are especially effective at protectingthe contents therein from UV radiation, allowing a longer shelf life ofthe product.

EXAMPLE 18

[0441] A multi-layer bottle is prepared wherein the exterior layer andthe innermost layer contacting the contents are composed of PET andwhich also comprises a barrier layer. When one or more of thebenzotriazole or s-triazines listed in Examples 16 and 17 areincorporated into any of the three layers at 0.5% by weight based on theweight of the resin, the contents of the bottle are effectivelyprotected from UV radiation.

EXAMPLE 19

[0442] A multi-layer bottle is prepared wherein the exterior layer andthe innermost layer contacting the contents are composed of HDPE andwhich also comprises a barrier layer. When one or more of thebenzotriazole or s-triazines listed in Examples 16 and 17 areincorporated into any of the three layers at 0.5% by weight based on theweight of the resin, the contents of the bottle are effectivelyprotected from UV radiation.

EXAMPLE 20

[0443] To separate polypropylene resin formulations are added 0.5% byweight of each of the benzotriazole and s-triazine stabilizers ofExamples 16 and 17. Each of the stabilized resin compositions are thenblow or injection molded into a polypropylene bottle having incorporatedtherein each of the UV absorbers. The polypropylene bottles areespecially effective at protecting the contents therein from UVradiation, allowing a longer shelf life of the product.

1. A method of protecting contents against the deleterious effects ofultraviolet radiation, which method comprises storing the contents in aclear or lightly colored rigid plastic container, which containercomprises an effective stabilizing amount of one or more compoundsselected from the group consisting of the durable hydroxyphenylbenzotriazole UV absorbers, wherein said benzotriazole UV absorbers areof formula (I), (II) or (III)

wherein G₁ and G₁′ are independently hydrogen or halogen, G₂ and G₂′ areindependently halogen, nitro, cyano, perfluoroalkyl of 1 to 12 carbonatoms, —COOG₃, —P(O)(C₆H₅)₂, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂,—N(G₃)—CO—G₃, E₃SO— or E₃SO₂—; or G₂′ is also hydrogen, G₃ is hydrogen,straight or branched chain alkyl of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms, E₁ is hydrogen, straight or branched chainalkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7to 15 carbon atoms, phenyl, or said phenyl or said phenylalkylsubstituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;or E₁ is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxygroups. when E₁ is phenylalkyl of 7 to 15 carbon atoms or phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms, G₂ may also be hydrogen, E₂ and E₂′ areindependently straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by one tothree alkyl of 1 to 4 carbon atoms; or E₂ and E₂′ are independently saidalkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atomssubstituted by one or more —OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁,—NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ is straight or branchedchain alkyl of 1 to 24 carbon atoms; or said alkyl or said alkenylinterrupted by one or more —O—, —NH— or —NE₄—groups or mixtures thereofand which can be unsubstituted or substituted by one or more —OH, —OE₄or —NH₂ groups or mixtures thereof; n is 1 or 2, when n is 1, E₅ is OE₆or NE₇E₈, or E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁, or straight orbranched chain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NE₁₁ andwhich can be unsubstituted or substituted by —OH or —OCO—E₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl, E₆ is hydrogen, straight orbranched chain C₁-C₂₄alkyl which is unsubstituted or substituted by oneor more OH, OE₄ or NH₂ groups, or —OE₆ is —(OCH₂CH₂)_(w)OH or—(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ is alkyl of 1 to 12 carbonatoms, E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring, E₅ is —X—(Z)_(p)—Y—E₁₅ wherein X is —O—or —N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkyleneinterrupted by one to three nitrogen atoms, oxygen atoms or a mixturethereof, or is C₃-C₁₂-alkylene, butenylene, butenylene, cyclohexylene orphenylene, each substituted by a hydroxyl group, m is zero, 1 or 2, p is1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively, E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—,forms together with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogenor methyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula

wherein the symbols E₁, G₂, X, Z, m and p have the meanings definedabove, and E₁₆ and E₁₇ independently of one another are hydrogen,C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or iscyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the case whereZ is ethylene, also forms ethylene, when n is 2, one of G₂ is alsohydrogen, E₅ is one of divalent radicals —O—E₉—O— or—N(E₁₁)—E₁₀—N(E₁₁)—, E₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene,cyclohexylene, straight or branched chain C₄-C₁₀alkylene which isinterrupted by —O— or by —CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—, E₁₀ beingstraight or branched chain C₂-C₁₂alkylene which may be interrupted by—O—, cyclohexylene, or

or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazine ring, E₁₄is straight or branched chain C₂-C₈alkylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O—, cycloalkylene, arylene or

where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene, E₁₁ is hydrogen, straight or branched chainC₁-C₁₈alkyl, C₅,-C₁₂cycloalkyl, straight or branched chainC₂-C₁₈alkenyl, C₆-C₁₄aryl or C₇-C₁₅aralkyl, E₁₂ is straight or branchedchain C₁-C₁₈alkyl, straight or branched chain C₃-C₁₈alkenyl,C₅-C₁₀cycloalkyl, C₆-C₁₆aryl or C₇-C₁₅aralkyl, E₁₃ is H, straight chainor branched C₁-C₁₈alkyl which is substituted by —PO(OE₁₂)₂, phenyl whichis unsubstituted or substituted by OH, C₇-C₁₅aralkyl or —CH₂OE₁₂, E₃ isalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms,alkyl substituted by alkoxycarbonyl of 2 to 9 carbon atoms, alkenyl of 3to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said arylsubstituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, and L is alkylene of 1 to 12 carbon atoms,alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene,α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene; and with theproviso that formula (I) does not represent5-chloro-2-(2-hydroxy-3,5-di-tert-butyl-phenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole or2-(2-hydroxy-3,5-di-α-cumyl)-2H-benzotriazole.
 2. (canceled)
 3. A methodaccording to claim 1 wherein said benzotriazole UV absorbers are offormula (I)

wherein G₁ is hydrogen, G₂ is hydrogen, cyano, chloro, fluoro, CF₃—,—CO—G₃, E₃SO— or E₃SO₂—, G₃ is straight or branched chain alkyl of 1 to24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, E₁ is phenylalkyl of7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkylsubstituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixturesthereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH— or —NE₄— groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —OE₄ or —NH₂ groups or mixturesthereof; E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one or two alkyl of 1 to 4carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where theperfluoroalkyl moiety is of 6 to 16 carbon atoms; or is a compound offormula (I) wherein, G₁ is hydrogen, G₂ is chloro, fluoro, CF₃—, E₃SO—or E₃SO₂—, E₁ is hydrogen or straight or branched alkyl of 1 to 24carbon atoms, E₂ is as defined above, and E₃ is straight or branchedchain alkyl of 1 to 7 carbon atoms; and with the proviso that formula(I) does not represent5-chloro-2-(2-hydroxy-3,5-di-tert-butyl-phenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole or2-(2-hydroxy-3,5-di-α-cumyl)-2H-benzotriazole.
 4. A method according toclaim 1 wherein said benzotriazole UV absorbers of formula (II) are ofthe formula (IIA)

wherein G₁ is hydrogen, G₂ is CF₃— or fluoro, E₁ is hydrogen, straightor branched alkyl of 1 to 24 carbon atoms or phenylalkyl of 7 to 15carbon atoms, when E₁ is phenylalkyl of 7 to 15 carbon atoms, G₂ mayalso be hydrogen, E₅ is —OE₆ or —NE₇E₈, or E₅ is —X—(Z)_(p)—Y—E₁₅wherein X is —O— or —N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z isC₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to three nitrogenatoms, oxygen atoms or a mixture thereof, or is C₃-C₁₂-alkylene,butenylene, butenylene, cyclohexylene or phenylene, each substituted bya hydroxyl group, m is 0, 1, 2 or 3, p is 1, or p is also zero when Xand Y are —N(E₁₆)— and —N(E₁₇)—, respectively, E₁₅ is a group—CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, forms together with E₁₇ agroup —CO—CH═CH—CO—, wherein E₁₈ is hydrogen or methyl, and E₁₉ ishydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ is hydrogen, C₁-C₁₂-alkyl ora group of the formula


5. A method according to claim 1 wherein said benzotriazole UV absorbersof formula (III) are of the formula (IIIA)

wherein G₂ is CF₃, G₂, is hydrogen or CF₃, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; and L is alkylene of 1 to 12 carbon atoms,alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene,α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene.
 6. A methodaccording to claim 1 wherein said benzotriazole UV absorbers are offormula (I)

wherein G₁ is hydrogen, G₂ is CF₃—, E₁ is phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, E₂ is straight orbranched alkyl chain of 1 to 24 carbon atoms, straight or branched chainalkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4carbon atoms; or E₂ is said alkyl of 1 to 24 carbon atoms or saidalkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁,—NH₂ or —NHCOE₁₁, or mixtures thereof, or said alkyl or said alkenylinterrupted by one or more —O— and which can be unsubstituted orsubstituted by one or more —OH, or is a compound of formula (I) wherein,G₁ is hydrogen, G₂ is CF₃—, E₁ is hydrogen, straight or branched alkylof 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and E₂is straight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —NH₂ or —NHCOE₁₁, or mixtures thereof, or said alkyl orsaid alkenyl interrupted by one or more —O— and which can beunsubstituted or substituted by one or more —OH.
 7. A method accordingto claim 1 wherein said benzotriazole UV absorbers of formula (II) areof the formula (IIA)

wherein G₁ is hydrogen, G₂ is CF₃—, E₁ is hydrogen, straight or branchedalkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, E₅is —OE₆ or —NE₇E₈ where E₆ is hydrogen, straight or branched chainC₁-C₂₄alkyl which is unsubstituted or substituted by one or more OHgroups, or —OE₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1to 12 and E₁₂ is alkyl of 1 to 12 carbon atoms, and E₇ and E₈ areindependently hydrogen, alkyl of 1 to 18 carbon atoms, straight orbranched chain C₃-C₁₈alkyl which is interrupted by —O—, —S— or —NE₁₁—,C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈together with the N atom are a pyrrolidine, piperidine, piperazine ormorpholine ring.
 8. A method according to claim 1 wherein saidbenzotriazole UV absorbers of formula (III) are of the formula (IIIA)

wherein G₂ is CF₃, G₂, is hydrogen or CF₃, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; and L is methylene.
 9. A method accordingto claim 1 wherein said benzotriazole UV absorbers are selected from thegroup consisting of (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;(d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];(e)methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-butyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];(f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid; (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(j)5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;(k) 5-octylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;(l)5-dodecylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(m)5-octylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;(o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;(p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(r)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;(s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;(u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;(v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;(y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole; (z)5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;(aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;(cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(dd) 5-chloro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole; (ee)5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;(ff) isooctyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;and (gg) 2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.10. A method according to claim 1 wherein said benzotriazole UVabsorbers are selected from the group consisting of (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;(g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;(j)5-butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole;(s)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;(x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;(aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;and (cc)5-phenylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.11-18. (canceled)
 19. A method according to claim 1 wherein saidcontainer comprises at least one hydroxyphenyl benzotriazole UV absorberand at least one further UV absorber selected from the group consistingof the tris-aryl-s-triazine UV absorbers, or which comprises a mixtureof two or more hydroxyphenyl benzotriazole UV absorbers.
 20. A methodaccording to claim 1 wherein said container additionally comprises atleast one UV absorber selected from the group consisting of2-(2-hydroxy-3,5-di-α-cumyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H -benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole and4,6-diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-s-triazine.
 21. A methodaccording to claim 1 in which said contents are selected from the groupconsisting of fruit juices, soft drinks, beer, wines, meats, vegetables,food products, dairy products, personal care products, cosmetics,shampoos, vitamins, pharmaceuticals, inks, dyes and pigments.
 22. Amethod according to claim 1 wherein said container is a mono- ormulti-layered container wherein each layer is comprised of one or morepolymers selected from the group consisting of polyesters, polyolefins,polyolefin copolymers, polyethylene-vinyl acetate, polystyrene,poly(vinyl chloride), poly(vinylidene chloride), polyamides,cellulosics, polycarbonates, polyethylene-vinyl alcohol, poly(vinylalcohol), poly(vinyl alcohol) copolymers, polystyrene-acrylonitrile,ionomers, partially hydrolyzed poly(vinyl acetate),poly(ethylene-co-vinyl alcohol), polyvinylidene chloride, polyurethanes,polyvinylidene chloride and polyepoxies.
 23. A method according to claim22 in which at least one layer is comprised of a polymer selected fromthe group consisting of poly(ethylene terephthalate), polyethylene andpolypropylene.
 24. A method according to claim 22 wherein the UVabsorbers are incorporated into a coating applied to the outer surfaceof the container.
 25. A method according to claim 1 in which the UVabsorbers are present from about 0.1 to about 20% by weight based on theweight of the plastic container.
 26. A method according to claim 1 wherethe container additionally comprises at least one coadditive selectedfrom the group consisting of anti-oxidants, other UV absorbers, hinderedamines, phosphites or phosphonites, hydroxylamines, nitrones,benzofuran-2-ones, thiosynergists, polyamide stabilizers, metalstearates, nucleating agents, fillers, reinforcing agents, lubricants,emulsifiers, dyes, pigments, optical brighteners, flame retardants,antistatic agents and blowing agents.